JPH10118408A - Powder flocculant composition and water treatment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain supernatant with a high clarity by adding a powder flocculant composition to a drain to be treated and flocculating a suspended fouling substance present in the drain by chemical reaction, in a short time, only through a stirring or dispersing action. SOLUTION: This powder flocculant composition consists of active silicon dioxide and alumina as main components, an inorganic powder particulate material with the maximum value of a zeta potential indicating at least, 15mV at the absolute value, a water-soluble aluminum compound, a water-soluble natural or synthetic polymer flocculant of a finer powder form than the routinely used type as a principal agent, an alkali metal carbonate and/or a cement powder particulate material as a pH value adjusting assistant and, if necessary, a bentonite or zeolite powder particulate material as a functional assistant. These components are uniformly mixed into a functional powder fluocculate composition. This flocculant composition is directly added and stirred, as a simple part, in a drain to be treated. After the completion of a flocculation reaction in the extensive pH range, flocks with superior morphological stability and dehydrating properties are separated and discharged to the outside of the water treatment system.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a powdery flocculant composition and a water treatment method using the same. More specifically, the present invention relates to a composition of the present invention formed by blending a specific substance, and a technique of applying the composition to water to be treated to aggregate pollutants in a short time and to form a floc which can be easily separated.

[0002]

2. Description of the Related Art Conventionally, as a coagulant generally used for wastewater treatment, an inorganic coagulant represented by a sulfuric acid band, polyaluminum chloride and the like, pH adjustment and, if necessary, a liquid natural or synthetic high coagulant. It is well known that a molecular coagulant is injected and stirred to separate polluted components from the wastewater as flocs. In most cases, the coagulant is handled as an aqueous solution for on-site work, so that the addition amount can be controlled relatively accurately even with a small amount.

[0003] On the other hand, however, the cost of storing and transporting the flocculant is high. In particular, the polymeric flocculant often dissolves completely on site, requiring a lot of time and labor for preparation, and also limits the effective action retention time. Suffering from various problems. Therefore, if a method that not only requires a considerable amount of time for the treatment as a whole but also ensures the reaction and residence time satisfactorily is adopted, a high initial cost is required as a facility opening cost, which is a favorable situation. Absent.

On the other hand, various studies have been made to improve the complexity of wastewater treatment using such a flocculant, and a method of selecting a conventional flocculant and a flocculant and a treatment condition suitable for this have been studied. In addition, modification of the flocculant itself is also being studied. For example, as a means of increasing the agglomeration treatment speed or improving the dehydration of the formed floc, in addition to the conventional aggregating agent, diatomaceous earth, clay, gypsum, limes, calcium carbonate, etc. are added as auxiliary agents. PH intended to improve process or wastewater treatment process
Various improvement measures have been studied and reported, such as development of a coagulant composition having a regulating function.

As one example, Japanese Patent Application Laid-Open No. 7-136409
In the patent publication, as a coagulant that can be discharged without the need for neutralization of the treated water, aluminum sulfate, calcium sulfate of a specific number of parts, an alkali metal carbonate as a pH adjuster, and cement as a sedimentation agent for coagulated floc, respectively. Examples of mixed compositions of various types such as zeolites or cationic coagulants are shown, and examples of treatment tests for mainly soil drainage and civil engineering muddy water are shown.

Usually, the wastewater to be subjected to the coagulation treatment is not only general factory wastewater, but also muddy water from a subway construction site, shield drainage in a tunnel construction, concrete drainage in a ready-mixed concrete site, and the like. Depending on the application case, the standard process cannot be adopted at all, and there are many cases where it is unavoidable to deal with more compact and simple equipment, and a wide range of applications such as a reliable and practical simple processing method It is up to you.

[0007]

As described above, according to the conventional processing method, the equipment employed is complicated,
In addition to requiring a considerable installation area for the processing equipment, the operation becomes complicated and the initial cost and running cost must be high.For example, direct treatment tends to be insufficient at civil engineering construction sites, etc. .

[0008] In addition, with respect to the remedies that have been proposed by using various types of coagulant compositions, when applied to a wide range of wastewater, a favorable floc is not always generated.
Further, a preferable supernatant water is not always obtained after separation of the formed flocs. As described above, many problems remain in the practical field, and it is still necessary to fundamentally study the development in terms of the mixed composition or the types and distribution of the components.

[0009]

Means for Solving the Problems In view of such circumstances, the present inventors have set out to solve the above-mentioned problems with ease of handling and low initial cost. Aggregates pollutants in wastewater in a short time,
We have intensively studied to develop a powdery flocculant composition that has good dehydration and stable flocs. As a result, a powdery flocculant composition which exerts a flocculating action on a relatively wide range of wastewater in a very short time, and the formed floc is stable, compact and has good dewatering properties, and wastewater treatment using this composition As a method, the following gist of the invention was made, and a patent application was already completed before filing the present application.

[0010] That is, the gist of the present invention is to provide inorganic powders containing active silicon dioxide and alumina as main components and exhibiting a maximum zeta potential of at least 15 mV in absolute value, and water-soluble natural or synthetic particles. And, if necessary, alkali metal carbonate and / or cement powder as a pH adjuster and, as a third component, bentonite-based soil mineral powder or zeolite-based powder. A powdery flocculant composition comprising a selected one as an additive selection substance, and a wastewater treatment method using the composition.

According to this prior invention, the present inventors can easily complete the flocculation reaction relatively simply by adding and stirring the specific powdery flocculant composition into the water to be treated, and separate the formed floc. It has been confirmed that by removing the wastewater from the system, it is possible to cope with the purification of various polluted wastewaters over a wide range. However, even with the composition of the present invention, it is often not always possible to obtain completely transparent treated supernatant water with respect to the water to be treated in a substantially stable colloidal state, such as strong emulsified suspension wastewater. Conventionally, treatment of such strongly emulsified wastewater is ultimately unavoidably entrusted to a combustion decomposition method or the like, and a high-cost method is used.

When the absolute value of the zeta potential is originally high, it is considered that the colloidal state is stable, and the present inventors consider that the charging assembly in such a stable region can be obtained by dissolving the composition of the present invention in water. We focused on the fact that the colloidal state, which is a constituent factor of emulsified suspension, can be destroyed by neutralizing with the electric charge generated in the above to lower the potential. The present inventors, from such a viewpoint,
For various types of water to be treated in a stable colloidal state,
The relationship between the expression of strongly acting zeta potential and its action and effect was studied diligently.

As a result, attention has been paid to the creation of a powder coagulant which is as balanced as possible and capable of expressing a strong zeta potential. We found that we could cope by strengthening in the dominant area and completed the present invention. That is, basically, it can be achieved by blending the composition of the preceding invention with a group of aluminum particles for promoting the formation of a polynuclear complex capable of supplying a large amount of positive charge and a pH adjusting function. .

[0014] The gist of the present invention is to provide an inorganic powder, water-soluble aluminum compound, water-soluble aluminum compound containing active silicon dioxide and alumina as main components and having a maximum zeta potential of at least 15 mV in absolute value. A powdery coagulant composition characterized by comprising a natural or synthetic polymer coagulant or the like as a main coagulant, and blending an alkali metal carbonate and / or cement powder with the coagulant; A powdery flocculant composition comprising at least one selected from a bentonite soil mineral powder or a zeolite powder in addition to the composition.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Among the chemicals constituting the composition of the present invention, there are known chemicals which have already been used as components of coagulants in the field of wastewater treatment. The composition of the present invention requires the formation of a specific special composition, and the composition of the present invention mutually utilizes the aggregating action based on the synergistic action of each component, and a coagulant known so far. Exerts an extremely powerful action and effect that could not be easily realized.

The first feature of the composition of the present invention is that the effect can be obtained only by adding a single powder coagulant composition to the treated wastewater, so that the conventionally used inorganic coagulants, inorganic salts and The effect obtained by introducing a polymer flocculant or the like into wastewater with complicated steps can be easily achieved. That is, the point is that the aggregation effect can be exhibited without impairing the properties of both the aggregation effect and the crosslinking effect. For this reason, it is particularly important that the polymer flocculant is incorporated in the active state as much as possible in the form of fine powder. As a result, the action time of the individual polymer flocculant fine particles almost coincides with the coexisting inorganic flocculant and other inorganic fine particles blended as other additives, and each component is added to the wastewater without being isolated. The agglutination reaction is completed in a very short time because the agglutination reaction is dissolved or dispersed.

The second feature of the composition of the present invention is that the flocculant has a very wide range of agglutination reaction and, for example, floc can be formed in a wide range such as pH 3 to 11 of the target wastewater, and a special p
The point is that it can be applied without requiring H adjustment. Although the reason for this is not clear, it is presumed that the absolute value of the zeta potential in water of the main component of the flocculant composition of the present invention is related to the point of maintaining a very high potential in a considerable pH range. I do. Therefore, floc can be substantially generated even if labor for pH adjustment equipment by injecting a chemical such as an acid or an alkali which is usually required in the coagulation treatment step is saved.

The third feature of the composition of the present invention is that the formed floc itself has an adsorbing effect, and the dissolved component CO
It is also useful for the adsorption removal of D, but by further blending at least one selected from bentonite soil mineral powder or zeolite powder, the above-mentioned main component of the present invention becomes the core of the generated floc, Adsorption and coagulation can be expected as synergistic effects with the respective components.
Furthermore, the removal of COD, which is a dissolved component in water, the stabilization of the obtained floc and the enhancement of dehydration are improved. In particular, an excellent effect is observed in combination with the bentonite soil mineral powder. This effect is advantageous in terms of a dewatering facility when this floc is separated as a cake and dewatered, and furthermore, a dewatered cake having a low water content is obtained, and as a result it is extremely useful for protection of the global environment.

The fourth feature of the composition of the present invention is that, as described above, since wastewater treatment can be carried out simply and reliably, wastewater generated in civil engineering and construction sites, etc., which was extremely difficult to treat directly at conventional sites, can be obtained. Not only is it possible to easily process and recycle the waste, but also at sites where conventional direct treatment is performed, more compact equipment and more reliable treatment is possible, and the amount of waste finally generated is lower than before. Is much less.

In the present invention, a powdery and granular material mainly composed of activated silicon dioxide and alumina having a high level of zeta potential as an absolute value, a water-soluble aluminum compound and a polymer coagulant, and an alkali metal as an essential component It is extremely important to use the carbonate and / or cement powder as a constituent element, and the combination of these essential components can exert the excellent effects of the present invention. Here, the method for obtaining the granular material mainly containing the active silicon dioxide and alumina specified in the present invention is not particularly limited.

For example, a composition in which the surface of fine particles has been activated by mixing and grinding a coarse particle mixture obtained by mixing a coarse particle mainly containing silicon dioxide and an alumina coarse particle under a high shearing force is used. A method of obtaining, a method of applying a chemical treatment to the surface of the once-pulverized and mixed granules, or a method of activating the surface of the pulverized and mixed granules by heat treatment, or an electric high-energy irradiation treatment or the like. The pulverized mixture particles are activated by a method of surface activation or the like to increase the absolute value of zeta potential in water.

The mixing ratio of silicon dioxide and alumina is set in a range in which the zeta potential is maintained in order to increase the absolute value of the zeta potential in water and to maintain a stable neutralizing ability of the colloid particles in water in a wide pH range. In the setting of the flocculant function, which is a minus advantage in some regions, and a plus advantage in a certain region, the present inventors have determined that at least 50% by weight of silicon dioxide and at least 5% by weight of alumina are required for a wide range of unspecified wastewater. On the other hand, it has been experimentally confirmed that it is particularly preferable. Further, by enhancing the positive advantage of the zeta potential mainly in the pH range of 4 to 8, the rapid coagulation effect, particularly in wastewater containing inorganic substances, and the transparency of the supernatant water can be effectively improved. In the present invention, a soluble aluminum compound is an essential component of the composition of the present invention.

The coarse particles containing silicon dioxide to be used in the present invention are commercially available quartz rocks or silica sands. A coarse particle preferably occupying about 99% of the pure silicon dioxide is selected. Mainly at least 250 in the crusher
It can be selected from objects that have been granulated to a degree of mesh under. These have a maximum value of about −40 mV when the zeta potential is measured in distilled water having a pH value of about 4 to 7. Further, natural quartzite or the like containing silicon dioxide and alumina as main components at the same time is selected, and an object having activity in these natural products is selected and pulverized in the same manner as described above, containing both essential components required for the present invention. Mixed powders can be obtained at once.

That is, from the naturally occurring quartzite, quartzite or siliceous schist-based minerals and similar ore fragments, a raw ore containing silicon dioxide and alumina as the main components required in the present invention is selected or appropriately mixed with components. The activated silicon dioxide and alumina used in the present invention may be activated by crushing under a high shearing force with a ball mill or the like, or, if necessary, further activating the surface of the crushed particles by chemical treatment or heat treatment. Can be obtained. The present invention can also be achieved by selecting and adopting powders obtained from these natural products and exhibiting a high level of absolute zeta potential as the object of the present invention.

Further, the alumina used in the present invention may be, for example, commercially available industrial activated alumina having a diameter of about 1.4 to 8 mm which is pulverized by a pulverizing mill. The zeta potential is usually about +30 mV at a pH of 4 to 5, and about -45 mV at a pH of 9 to 10. The measurement of zeta potential and the like is generally performed by using a laser Doppler electrophoresis method.

The fine powdery polymer flocculant used in the present invention may be either natural or synthetic. In particular, nonionic, anionic, cationic and amphoteric polymer flocculants are used for synthetic ones. In addition, these synthetic polymer flocculants can sufficiently exert the effects of the present invention even if the same type or different types of various polymer flocculant mixtures are used, if necessary, and any of commercially available products can be used. Can be targeted. On the other hand, various polysaccharides can be used in natural products. In particular, fine powder obtained by freeze-drying or spray-drying an aqueous solution of acidic polysaccharide polymer mainly containing β-1,3 glucan cultured by microorganisms is used. preferable.

In order to obtain the powdery flocculant composition of the present invention,
It is important to homogenously pulverize and mix mainly the above-mentioned powdered granules mainly composed of activated silicon dioxide and alumina and a powdery polymer flocculant. At this time, it is advantageous to the composition of the present invention that the particle size distribution of each component is mainly at least 80 mesh under, and preferably as fine as possible. In particular, it is extremely important for the composition of the composition of the present invention that the particle size of the fine powder of the polymer flocculant is as fine as 100 mesh under in the composition product. In the case of wastewater treatment with coarse particles,
If the uniform dissolution rate characteristic is not exhibited in the flocculant effect surface of the present invention, the speed of the flocculation reaction surface is adversely affected, and the partial stickiness of the formed floc is unnecessarily increased. There are concerns.

In the present invention, a powdery flocculant composition having a specific composition can be easily obtained by simultaneously mixing the specific compounds constituting the present invention in powder form and mixing them uniformly. As the composition ratio of the composition, all of them need to correspond variably, but as a basic composition, the main component is activated silicon dioxide and alumina which are coagulant components, and the absolute value of the maximum value of the zeta potential is at least 15 mV. Preferably, it is determined by the blending amount of a powdery or granular material exhibiting 20 mV, a water-soluble aluminum compound and a natural or synthetic polymer flocculant.
In addition, an alkali metal carbonate as a pH adjuster and / or
Or as cement powder and third component if necessary,
One selected from bentonite soil mineral powder or zeolite powder is blended as an essential optional additive.

Assuming that each material is blended in the powder coagulant representative of the present invention, the constituent weight ratio of the whole composition is 10%.
Assuming 0%, 20 to 89.5% by weight of a granular material mainly containing active silicon dioxide and alumina specified in the present invention, 5 to 50% by weight of a water-soluble aluminum compound, and a water-soluble natural or synthetic water-soluble compound. 0.5 to 30% by weight of a polymer coagulant and 5 to 30% by weight of an alkali metal carbonate and / or cement powder are uniformly mixed to obtain a composition.

With the composition ratio of the composition shown here, the whole is 1
First, it is necessary to set the content of the polymer flocculant to at least 0.5% by weight, and if the content is less than this, the effect is slow or the reaction time is extremely long. On the other hand, a blending amount of 30% by weight or more is not preferred because the dewatering property of the formed floc after the reaction is extremely deteriorated. On the other hand, in the composition of the composition, the blending ratio is preferably adjusted to maintain the important zeta potential, which is the base of the present invention, and to achieve a well-balanced and uniform characteristic effect as the composition. It is shown in%.

That is, the compounding amount of the powdered granules containing the active silicon dioxide and alumina as the main components is determined by the compounding amount of the polymer flocculant, the water-soluble aluminum compound and the pH.
In view of the amount of the alkali metal carbonate and / or cement powder having a regulating action, the content is preferably 20 to 89.5% by weight. When it is necessary to enhance the positive effect of the zeta potential mainly in the pH range of 4 to 8, the amount of the water-soluble aluminum compound is adjusted, but the range is 5 to 50% by weight. Is preferable. Further, the amount of the alkali metal carbonate and / or cement powder having a pH adjusting effect is preferably 5 to 30% by weight, respectively.

On the other hand, when the third component is added to these compositions and at least one selected from bentonite soil mineral powder and zeolite powder is added and blended, the constituent weight ratio of the whole composition Need to be adjusted.
In this case, the total composition is 100% by weight, the blending amount of the above-mentioned polymer flocculant is 0.5 to 30% by weight, and the granular material mainly composed of active silicon dioxide and alumina specified in the present invention is added thereto. 20 to 94.5% by weight, 5 to 50% by weight of a water-soluble aluminum compound, 5 to 30% by weight of alkali metal carbonate and / or cement powder, and further, bentonite soil mineral powder and zeolite powder 5 to 3 at least one selected from granules
0% by weight is uniformly mixed to form the composition.

With the composition ratio of the composition shown here, the composition used as the basis of the present invention has a dehydration property of formed floc and a C content in the treated water.
In the case of enhancing the adsorptivity of the OD component, at least one selected from bentonite soil mineral powder and zeolite powder as the third component in addition to various necessary flocculant main components and flocculant aid components Is blended.
At this time, it is necessary to add at least 5% by weight alone or as a mixture. However, if the content is more than 30% by weight, the compositional balance of the composition is disturbed, so that the coagulation effect, which is the basis of the present invention, is unpreferably reduced.

As the alkali metal carbonate or cement powder used as the pH adjuster in the present invention, sodium carbonate, sodium bicarbonate, potassium carbonate, Portland cement and the like are particularly preferable. The bentonite soil mineral powder used as the third component in the present invention is mainly composed of silicic acid and alumina, and contains trace amounts of calcium oxide, potassium oxide, magnesium oxide, etc. It is a granular material made from an alkaline soil mineral, and the particle diameter of the constituent powder is preferably about 200 mesh pass to about 250 mesh on.

The zeolite-based powder is mainly made by crushing natural soil minerals. The main constituents are alkali metals such as sodium and potassium, and the main constituents are alkaline earth metals such as calcium and magnesium. Is an aluminosilicate mineral containing water molecules in the form of water of crystallization. The powders and granules employed in the present invention include:
Either natural or synthetic zeolite powder products can be targeted.

The field of application of the powdery flocculant composition of the present invention is not particularly limited, and is not limited to wastewater treatment and recycle of treated water at civil engineering construction sites, but also bilge wastewater, ballast wastewater, and general oil-containing wastewater. It can be used as a coagulating sedimentation treatment agent for pre-treatment of industrial wastewater treatment such as steel rolling wastewater, water-soluble cutting oil wastewater, and other biological treatment processes. In addition, it is extremely useful in a wide range of fields, such as primary treatment of concentrated wastewater and addition as a flocculant at the time of dewatering of excess sludge and digested sludge drawn out of biological treatment, and thus greatly contributes to the protection of the global environment. is there.

Hereinafter, the present invention will be described with reference to Examples and Comparative Examples.

【Example】

Example 1 Silica sand containing silicon dioxide at a high purity of about 99.8% was pulverized by a pulverizing mill so as to have a size of 350 mesh under (particle size of about 44 μm). 35% by weight, about 99.8% milled to 250 mesh under (particle size of about 60 μm) and 10% by weight of high-purity γ-alumina powder, and aluminum sulfate particles having an average of about 150 μm 30% by weight, non-ionic NP800N (hereinafter abbreviated as A) or strong cationic KP1200B (hereinafter abbreviated as B) manufactured by Diafloc as a flocculant
Any one of the synthetic polymer flocculants is selected and added in an amount of 5% by weight, and sodium carbonate having an average particle size of about 300 μm is mixed at a ratio of 20% by weight to form a crude mixture having a total amount of 100 g. This was further uniformly pulverized and mixed with a pulverization mixer at about 3000 revolutions for 1 minute to obtain a composition of the present invention having an average particle size of about 44 μm.

Using the obtained composition of the present invention as raw water,
(S content: about 1200 mg / l) To a milky white glass polishing wastewater with a pH of 6.9, various concentrations as shown in Table 1 were added, and a flocculation test was conducted using a jar tester (150 rpm) to confirm the floc generation state. Performed as 1 to 5. The evaluation was carried out based on the stirring reaction time (sec) from the addition of the flocculant to the generation of the stable floc, the diameter (mm) of the floc formed by visual observation, the Toyo Filter Paper No. The clarity (kaolin turbidity), pH value, and the like of the filtrate using 5A filter paper were measured.
In Experimental Examples 1 to 3, the polymer coagulants A and 4 and 5 used the polymer flocculant B.

The mixed powder of silica powder having a purity as high as about 99.8% of silicon dioxide and γ-alumina powder having a purity as high as that of the silica powder containing the silicon dioxide component at the above-mentioned predetermined ratio is used. The zeta potential was measured by laser Doppler electrophoresis, and the average of four measurements was minus 25.3.
mV. As a specific measuring method, a small amount of a powder sample is put into about 30 ml of distilled water, subjected to an ultrasonic dispersion treatment for about 3 minutes, and then allowed to stand for 30 minutes, and the supernatant is filtered through a 5 μm filter. Afterwards the zeta potential was measured. The pH of the measurement supernatant was 6.7 to 6.8. The experimental results and evaluations of the above-described embodiment are as shown in Table 1 below.

[0040]

[Table 1]

From the results in Table 1 above, the reaction time by stirring, the diameter of the formed floc observed by visual observation, the clarity of the filtrate, the pH value, and the like were all satisfactory in each of Experimental Examples 1 to 5. It can be seen that the composition of the present invention exhibits a suitable coagulation effect.

Comparative Example 1 For comparison with the present invention, in Comparative Experimental Example 1, a mixed powder of a silicon dioxide component and an aluminum powder of the components of Example 1 was used as a similar composition outside the scope of the present invention. The zeta potential at the time of mixing a predetermined amount in the same manner as in Example 1 was measured four times using powdery and granular materials having low activity, and the average value was minus -6.
The operation was carried out under the same conditions as in Experimental Example 1 of Example I except that the coagulant of A and 2 mV were used. In Comparative Experimental Example 2, an industrial commercial product, about 10% PAC solution and Diafloc's nonionic polymer flocculant NP800N were used.
(0.1% solution), and the pH was adjusted with a sodium hydroxide solution diluted with distilled water. Further, in Comparative Experimental Example 3, an experiment was performed in the same manner as in Comparative Experimental Example 2, except that the target raw water was diluted twice with tap water. Under these conditions, a test with a jar tester was performed on the same polishing waste water as used in Example 1 until flocs were generated, and the evaluation results are shown in Table 2 below.

[0043]

[Table 2]

From the results in Table 2 above, it was found that a flocculant composition similar to the present invention did not provide a sufficient effect, and that no floc was generated even when the raw water was treated as it was in the conventional method. By diluting twice with tap water and adjusting the pH, generation of some flocs was observed.
However, it turns out that these results are extremely disadvantageous when compared with the method of the present invention.

Example 2 A natural quartzite composed of about 80% of silicon dioxide, about 10% of an alumina component and about 10% of other components was subjected to 25 ball milling.
It was pulverized so as to have 0 mesh under (particle size of about 60 μm) to obtain a rattan powder. When the zeta potential of this powder was checked in the same manner as in Example 1, the average value was minus 29.6 mV. 55% by weight of the rock powder prepared here, 20% by weight of aluminum sulfate particles having an average of about 150 μm, and a strong cationic synthetic polymer flocculant KP1 manufactured by Diafloc as a commercially available flocculant.
10% by weight of 200B and 15% by weight of sodium carbonate having an average particle size of about 300 pm.
g of crude mixture was made. The obtained crude mixture was further uniformly pulverized and mixed by a pulverization mixer of about 3000 revolutions for 1 minute to obtain a composition of the present invention having a size of 350 mesh under (average particle size of about 44 μm).

Experimental Example 6 Using the prepared composition of the present invention.
To the raw water in various proportions as shown in
A flocculation test was performed in the same manner as in Example 1 in order to confirm the occurrence of flocs using a jar tester (150 rpm). For raw water, SS content is about 1800mg / l)
Oil-containing wastewater having a pH of 6.1 and having a blackish brown color was used in an automobile repair shop. The evaluation was performed in the same manner as in Example 1, and the results are shown in Table 3 below.

[0047]

[Table 3]

From the results in Table 3 above, the reaction time by stirring, the diameter of the formed floc by visual observation, the clarity of the filtrate, the pH value, etc. were determined in each of Experimental Examples 6 to 10.
The results of the examples of the present invention were all satisfactory, and it was confirmed that the composition of the present invention was extremely excellent.

Comparative Example 2 For comparison with the present invention, in Comparative Experimental Example 4, an experiment was performed under the same conditions as in Experimental Example 7 of Example 2 using a similar composition outside the scope of the present invention. That is, the silicon dioxide content is reduced to about 80
%, An alumina component of about 10%, and other about 10% of natural quartzite were pulverized with a ball mill so as to have a 250 mesh under (particle size of about 60 μm) to obtain a rattan powder. When the zeta potential of this powder was checked in the same manner as in Example 1, the average was -1.
0.2 mV was shown.

55% by weight of the rock powder prepared here, 20% by weight of aluminum sulfate particles having an average of about 150 μm, and 10% of a strong cationic synthetic polymer flocculant KP1200B of Diafloc as a commercially available flocculant. % By weight and sodium carbonate having an average particle size of about 300 μm were mixed at a ratio of 15% by weight to prepare a crude mixture having a total amount of 100 g.
The obtained crude mixture was further pulverized and mixed uniformly with a pulverization mixer of about 3000 revolutions for 1 minute, and employed as a similar composition having a 350 mesh under (average particle size of about 44 μm) outside the range of the present invention.

On the other hand, in Comparative Example 5, an industrial commercial product was used.
About 10% PAC solution and Diafloc nonionic polymer flocculant NP800N (0.1% solution) were used in combination, and the pH was adjusted with a sodium hydroxide solution diluted with distilled water. Furthermore, in Comparative Experimental Example 6, an experiment was performed in the same manner as in Comparative Experimental Example 4, except that the target raw water was diluted three times with tap water. Under these conditions, various ratios as shown in Table 4 below were added to the raw water, and a flocculation test was performed in the same manner as in Example 1 to check the occurrence of flocs using a jar tester (150 rpm). For raw water, SS content about 1800mg /
1, oil-containing wastewater having a pH of 6.1 and having a blackish brown color was used. The evaluation was performed in the same manner as in Example 1, and the results were as shown in Table 4 below.

[0052]

[Table 4]

From the results shown in Table 4, similar compositions outside the scope of the present invention cannot provide the same level of processing effects as those of the examples of the present invention. Further, in the conventional method, considerable time and a means such as pH adjustment were taken to treat raw water to generate flocs, but only insufficient results were obtained. Therefore, when the results of these comparative examples are compared with the method of the present invention, the agglomerated composition of the present invention is extremely excellent in agglutinating reactivity, and the shortening of processing time and the avoidance of complexity, which are difficult to compare with the conventional method. It is clear that is very advantageous in

Example 3 Silica sand containing silicon dioxide at a high purity of about 99.8% was pulverized with a pulverizing mill to a size of 350 mesh under (particle size of about 44 μm). The powder was 75% by weight, about 99.8% milled to 250 mesh under (particle size of about 60 pm) and 25% by weight of high-purity γ-alumina powder, and this was further added to about 300 minutes for about 300 minutes.
The mixture was uniformly pulverized and mixed with a pulverization mixer of 0 rotation to obtain a mixed powder having an average particle size of about 44 μm. The zeta potential was measured by the same method as in Example 1 and found to have an average value of minus 28.8 mV.

40% by weight of the mixed powder, on average about 1%
20% by weight of 50 μm aluminum sulphate powder, 5% by weight of KF1200B, a strong cationic synthetic polymer flocculant from Diafloc as a commercially available flocculant, having an average particle size of about 30%.
0 μm sodium carbonate at 15% by weight, commercially available average about 7
A powder of the present invention in which a bentonite powder having a particle size of 5 μm is mixed at a ratio of 20% by weight, and is uniformly ground and mixed by a grinding mixer of about 3000 revolutions for 1 minute to have an average particle size of about 44 μm. 100 g of a liquid composition was obtained.

Using the obtained composition of the present invention as raw water,
An agglutination test was conducted by adding a variety of ratios to the milky white glass polishing wastewater having an S content of about 1200 mg / l and a pH of 6.9 as shown in Table 5 and using a jar tester (150 rpm) to check the state of floc generation. 11 to 15
It was carried out as. The results of these experiments were evaluated by determining the stirring reaction time (sec) from the addition of the flocculant to the generation of stable flocs, the diameter (mm) of the flocs formed by visual observation, and Toyo Filter Paper No. The clarity (kaolin turbidity) and the pH value of the filtrate with 5A filter paper were evaluated. The experimental results of these examples are as shown in Table 5 below.

[0057]

[Table 5]

From the results shown in Table 5, the reaction time by stirring, the diameter of the floc formed by visual observation, the clarity of the filtrate, the pH value, etc. are all satisfactory in each of Experimental Examples 12 to 14. In particular, all of the examples were similarly made of Toyo Filter Paper No. It was confirmed that the filtration residue after filtration with the 5A filter paper adhered little to the filter paper, and was excellent in dehydration. Therefore, it is understood that the composition of the present invention is extremely innovative.

Comparative Example 3 For comparison with the present invention, Comparative Examples 7 to 9 used similar compositions outside the scope of the present invention. That is, 75% by weight of a powder obtained by pulverizing a silica sand containing a silicon dioxide component with a pulverizing mill so as to have a particle size of about 350 μm (about 44 μm) has a particle size of about 250% (about 60 μm). Approximately 9 milled to
9.8% and 25% by weight of high-purity γ-alumina powder were further uniformly pulverized and mixed by a pulverization mixer of about 3000 revolutions for 1 minute to prepare a mixed powder having an average particle size of about 44 μm. . The zeta potential was measured in the same manner as in Example 1, and a powder having an average value of minus 8.8 mV was selected.

Except for using this mixed powder, a composition similar to the present invention was produced in exactly the same composition combination as in Example 3, and the experimental raw water used in Example 3 is shown in Table 6 below. Table 6 shows the results of comparative processing experiments performed by changing the amount of addition as described above.

[0061]

[Table 6]

From the results shown in Table 6, similar compositions outside the scope of the present invention do not provide the same treatment effects as those of the examples of the present invention. Therefore, comparing the results of these comparative examples with the method of the present invention, it was confirmed that the agglomerated composition of the present invention was extremely excellent in agglutination reactivity.

Example 4 Silica sand containing silicon dioxide in a high purity of about 99.8% was pulverized with a pulverizing mill to a size of 350 mesh under (particle size of about 44 μm). The powder was 75% by weight, about 99.8% milled to 250 mesh under (particle size of about 60 μm) and 25% by weight of high-purity γ-alumina powder, and this was further added to about 300 minutes for about 300 minutes.
The mixture was uniformly pulverized and mixed with a pulverization mixer of 0 rotation to obtain a mixed powder having an average particle size of about 44 μm. The zeta potential was measured in the same manner as in Example 1 and the average was minus 2
It showed 8.8 mV.

30% by weight of the mixed powder, on average about 1%
30% by weight of 50 μm aluminum sulphate powder, strong cationic KP1200B alone (hereinafter abbreviated as C) or KP1200B and amphoteric KA405D mixed in a ratio of 7: 3 as a commercially available coagulant of Diafloc (Hereinafter abbreviated as D) in an amount of 10% by weight, 20% by weight of sodium carbonate having an average particle diameter of about 300 μm, and 1% of commercially available bentonite powder having an average particle diameter of about 75 μm.
0% by weight, and uniformly pulverized and mixed with a pulverization mixer of about 3000 revolutions for 1 minute to give an average particle size of about 44 μm
By adjusting back and forth, 100 g of the powdery composition of the present invention was obtained.

Using the obtained composition of the present invention as raw water,
S content was added to milky white effluent, which is a wire-drawing copper process water having a pH of about 1300 mg / l and a pH of 7.3, at various ratios as shown in Table 7, and the occurrence of floc by a jar tester (150 rpm) was confirmed. Experiment 1
6-20. The stirring reaction time (sec) from the addition of flocculant to the generation of stable floc
Diameter (mm) of generated floc by visual observation, Toyo Filter Paper N
o. The clarity (kaolin turbidity) and the pH value of the filtrate with 5A filter paper were evaluated. In Experimental Examples 16 to 18, the polymer coagulant C was used, and in Examples 19 to 20, the polymer coagulant D was used. The experimental results of these examples were as shown in Table 7 below.

[0066]

[Table 7]

From the results shown in Table 7 above, the reaction time by stirring, the diameter of the formed floc by visual observation, the clarity of the filtrate, the pH value, and the like were all satisfactory in each of Experimental Examples 16 to 20, In particular, all of the examples were similarly made of Toyo Filter Paper No. It was confirmed that the filtration residue after filtration with the 5A filter paper adhered little to the filter paper, and was excellent in dehydration. Therefore, it is understood that the composition of the present invention is extremely innovative.

Comparative Example 4 For comparison with the present invention, a similar composition outside the scope of the present invention was used except that the same mixture of silica sand and γ-alumina powder as used in Comparative Example 3 was used. A composition similar to the present invention was produced in the same composition combination as in Example 4, and a comparative treatment experiment was performed in the same manner as for the raw water used in Example 4 with the addition amounts shown in Table 8 below. It was implemented and evaluated. Here, Comparative Experimental Examples 10 and 11 are examples using the polymer flocculant C, and Comparative Experimental Example 12 is an example using the polymer flocculant D.

[0069]

[Table 8]

From the results shown in Table 8 above, it was not possible to obtain the same clear supernatant water as in the examples of the present invention with similar compositions outside the scope of the present invention. Therefore, comparing the results of these comparative experimental examples with the method of the present invention, it was confirmed that the agglomerated composition of the present invention was more excellent in agglutination reactivity.

[0071]

Industrial Applicability The powdery flocculant composition of the present invention comprises an inorganic powdery material comprising active silicon dioxide and alumina as main components and having a maximum zeta potential of at least 15 mV in absolute value, a water-soluble Aluminum compound, natural or synthetic polymer flocculant as main ingredient, alkali metal carbonate and / or cement powder as pH adjustment aid, and bentonite or zeolite powder as functional aid when necessary It is a self-contained powdery wastewater treatment agent which is a composite composition constituted by mixing bodies. However, the coagulation reactivity of the composite composition in the wastewater to be treated has uniformity, and is lower than the conventional stepwise reaction method using a coagulant.
An industrial effect that is extremely excellent in terms of reaction time and work simplicity is exhibited.

That is, in the present invention, the reactivity of the other components which act synergistically in the composition with an organic polymer flocculant having a moderate reactivity is compared with that of a fine powder which has not been conventionally carried out. By compounding in the powder composition as
The complete treatment can be achieved by simply adding and stirring the powdered flocculant composition of the present invention to the wastewater to be treated. As a result, the coagulation and sedimentation treatment of various wastewaters can be performed extremely simply, and greatly contributes industrially in various wastewater treatment fields.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] December 10, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction contents]

In the present invention, a powdery flocculant composition having a specific composition can be easily obtained by simultaneously mixing the specific compounds constituting the present invention in powder form and mixing them uniformly. As the composition ratio of the composition, all of them need to correspond variably, but as a basic composition, the main component is activated silicon dioxide and alumina which are coagulant components, and the absolute value of the maximum value of the zeta potential is at least 15 mV. Preferably, it is determined by the blending amount of a powdery or granular material exhibiting 20 mV, a water-soluble aluminum compound and a natural or synthetic polymer flocculant.
In addition, an alkali metal carbonate as a pH adjuster and / or
Or cement powder , as a mixing aid for the basic composition
Calcium compounds, titanium dioxide, sodium sulfate, diatomaceous earth
Any inert substance and , if necessary, one selected from bentonite soil mineral powder or zeolite powder as the third component are blended as essential optional additives.

Claims (12)

[Claims] An inorganic powder, a water-soluble aluminum compound, a water-soluble natural or synthetic polymer containing active silicon dioxide and alumina as main components and having a maximum zeta potential of at least 15 mV in absolute value. A powdery coagulant composition comprising a coagulant or the like as a main coagulant, and an alkali metal carbonate and / or cement powder blended therein. 2. The powder according to claim 1, wherein at least one selected from the group consisting of bentonite soil mineral powder and zeolite powder is added to the composition when the powdery flocculant is constituted. Body coagulant composition. 3. The powdery coagulant composition according to claim 1, wherein said zeta potential is at least 20 mV. 4. The powdery flocculant composition according to claim 1, wherein said active silicon dioxide comprises at least 50% by weight and said alumina comprises at least 5% by weight. 5. The powdery flocculant composition according to claim 1, wherein the water-soluble aluminum compound is any one of aluminum sulfate, aluminum chloride and polyaluminum chloride. 6. The powdery flocculant composition according to claim 1, wherein a nonionic or cationic natural or synthetic polymer flocculant is used as said water-soluble polymer flocculant. 7. The natural polymer flocculant as β-1,3
The powdery flocculant composition according to any one of claims 1 to 6, wherein an acidic polysaccharide polymer mainly containing glucan is used. 8. The powdery flocculant composition according to claim 1, wherein sodium carbonate, sodium bicarbonate, potassium carbonate or Portland cement is used as the alkali metal carbonate and / or cement powder. 9. The powder according to claim 1, wherein said powder has a particle size of at least 1
The powdery flocculant composition according to any one of claims 1 to 8, comprising a small particle size of 00 mesh under. 10. Assuming that the composition constitutes 100% by weight of the total composition, 20 to 89.5% by weight of said inorganic powder containing activated silicon dioxide and alumina as a main component and 5 to 50% by weight of a water-soluble aluminum compound. 5 to 30% by weight of a water-soluble natural or synthetic polymer flocculant, and 5 to 30% by weight of an alkali metal carbonate and / or cement powder. The powdery flocculant composition according to any one of claims 1 to 9, wherein 11. The composition of the present invention, wherein the composition weight ratio is 100%, 20 to 84.5% by weight of said inorganic powder mainly composed of activated silicon dioxide and alumina, and 5 to 50% by weight of a water-soluble aluminum compound. By weight, 0.5 to 30% by weight of a water-soluble natural or synthetic polymer flocculant, 5 to 30% by weight of alkali metal carbonate and / or cement powder, and bentonite soil mineral powder and zeolite At least one selected from system-based powders
2. The composition of claim 1, wherein the composition is homogeneously mixed to form a composition.
11. The powdery flocculant composition according to any one of items 10 to 10. 12. A water treatment method comprising adding the powdery coagulant composition according to any one of the above-mentioned claims to the water to be treated, and causing a coagulation reaction with stirring.